CN114824202A - FeS with multi-core shell structure 2 Preparation method and application of @ C nanocapsule material - Google Patents
FeS with multi-core shell structure 2 Preparation method and application of @ C nanocapsule material Download PDFInfo
- Publication number
- CN114824202A CN114824202A CN202210382823.XA CN202210382823A CN114824202A CN 114824202 A CN114824202 A CN 114824202A CN 202210382823 A CN202210382823 A CN 202210382823A CN 114824202 A CN114824202 A CN 114824202A
- Authority
- CN
- China
- Prior art keywords
- fes
- shell structure
- core shell
- nanocapsule
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000002088 nanocapsule Substances 0.000 title claims abstract description 41
- 239000011258 core-shell material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 11
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 229920001690 polydopamine Polymers 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 238000005406 washing Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000005530 etching Methods 0.000 description 10
- 239000012467 final product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000002775 capsule Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a FeS with a multi-core shell structure 2 The preparation method and application of the @ C nanocapsule material comprise the following steps: fe production using ammonium sulfate-assisted hydrothermal process 2 O 3 A nanocapsule template; covering polydopamine on the surface of the product obtained in the step (1), and sintering in argon to obtain Fe 3 O 4 @ C nanocapsules; treating the product with HF diluent, stirring and centrifuging to obtain the Fe with the multi-core shell structure 3 O 4 @ C nanocapsules; product is in H 2 Calcining in S atmosphere to obtain FeS with a multi-core shell structure 2 @ C nanocapsule material. FeS with multi-core shell structure prepared by the invention 2 The @ C nanocapsule material has excellent electrochemical performance and is a promising potassium ion battery negative electrode material.
Description
Technical Field
The invention relates to a preparation method and application of a potassium ion battery cathode material, in particular to FeS with a multi-core shell structure 2 A preparation method and application of the @ C nanocapsule material.
Background
In the field of electrochemical energy storage, Lithium Ion Batteries (LIBs) are the most widely used energy storage devices by virtue of high operating voltage, large energy density and long cycle life. The commercial application range of LIBs is gradually expanding from portable electronic products to electric vehicle applications, and is also rapidly developing, which raises concerns about the persistence and price increase of lithium resources. On the other hand, the ever-increasing market for renewable energy storage from solar, wind, hydroelectric and other sources has led to a pressing need for more reliable and lower cost alternatives to expensive LIBs. Recently, Potassium Ion Batteries (PIBs) have been proposed and considered as one of the most promising alternatives to LIBs, because of the high natural abundance of potassium resources, which have lower standard redox potentials (Li/Li) compared to Na + =-3.040V、K/K + =-2.936V、Na/Na + -2.714V vs SHE), and similar to the electrochemical properties of lithium, are expected to play a dominant role in the field of large-scale energy storage.
FeS 2 Has the characteristics of high theoretical capacity, low preparation cost, environmental protection and the like, and is an ideal cathode material of the potassium ion battery. However, this material is a sulfide, which is poorly conductive. In addition, the volume change is large in the process of inserting and removing potassium, so that the structure of the material is easily damaged, and the cycle stability is deteriorated. In addition, the polysulfide dissolution problem generated by the discharge process causes a rapid capacity fade. Thus FeS 2 The development and application of materials are limited by poor cycling stability and rate capability.
Carbon coating is one of the most effective strategies to solve the above problems. FeS coated with conductive carbon 2 The overall electronic conductivity can be improved, and the volume expansion and sulfide dissolution of the coating layer can be limited to a certain extent. Nevertheless, FeS obtained by conventional methods 2 The particles are large, the substances in the particles are difficult to exert activity,often exhibit a lower reversible capacity. And the outer carbon coating is easily broken after long-time circulation, which results in structural damage.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide FeS with a multi-core shell structure with excellent cycle performance and rate performance 2 A preparation method of the @ C nanocapsule material.
Another object of the present invention is to provide FeS having the above-mentioned multi-core-shell structure 2 Application of @ C nanocapsule material.
The technical scheme is as follows: the FeS with the multi-core shell structure 2 The preparation method of the @ C nanocapsule material comprises the following steps:
(1) fe production using ammonium sulfate-assisted hydrothermal process 2 O 3 A nanocapsule template;
(2) coating polydopamine on the surface of the product obtained in the step (1), and sintering in argon to obtain Fe 3 O 4 @ C nanocapsules;
(3) treating the product in the step (2) by HF diluent to obtain Fe with a multi-core shell structure 3 O 4 @ C nanocapsules;
(4) subjecting the product of step (3) to reaction in H 2 Calcining in S atmosphere to obtain FeS with a multi-core shell structure 2 @ C nanocapsule material.
Further, in the step (1), ammonium sulfate is added into the hydrothermal solution, and the hydrothermal solution is 3mol L -1 The iron source of the sodium hydroxide solution is FeCl 3 。
Further, the hydrothermal temperature of the step (1) is 80-100 ℃, and the hydrothermal time is 4-6 days.
Further, Fe in the step (2) 2 O 3 The concentration of the dispersion is 5-8 mmol L -1 。
Further, the temperature of carbonization in the argon in the step (2) is 600-700 ℃.
Further, the concentration of the HF diluent in the step (3) is 2-4 mmol L -1 。
Further, in the step (3), magnetic stirring treatment is carried out, the reaction time is 10-30 min, and the optimal reaction time is 20 min.
Further, the sintering atmosphere in the step (4) is H 2 The volume ratio of the S/Ar mixed gas is 10: 90.
Further, the calcining temperature in the step (4) is 300-400 ℃, and the calcining time is 3-5 hours.
Further, the method for calcining in the step (4) comprises the following steps: drying the product obtained in the step (3), pressing the product into powder, placing the powder into a tube furnace, and placing the powder in the tube furnace for 2 ℃ min -1 The temperature is raised to 300-400 ℃ at a speed and then kept for 3-5 h.
The FeS with the multi-core shell structure prepared by the preparation method 2 The application of the @ C nanocapsule material as a potassium ion battery negative electrode material.
The invention uses capsule-shaped Fe in the synthesis process 2 O 3 As a template, poly-dopamine is coated on the surface of the poly-dopamine by using polymerization reaction and then carbonized to obtain Fe 3 O 4 @ C nanocapsules and etching away part of the Fe in HF dilution 3 O 4 Finally at H 2 Sintering in the mixed gas of S and Ar to obtain FeS 2 @ C nanocapsule material. The product has a multi-core shell nanocapsule structure. By adjusting the time of HF treatment, the size of the internal cavity and the FeS can be optimized 2 Density of the nanoparticles. In addition, the method uses H 2 The sulfuration reaction is initiated by the mixed gas of S and Ar, the reaction temperature is low, the process is simple, and the product purity is high.
The method can prepare FeS with a multi-core shell structure 2 The material of the @ C nanocapsule has an outer carbon shell which is favorable for improving the overall conductivity of the material through electron transmission and can also serve as a protective layer to buffer FeS 2 The volume expansion and polysulfide dissolution inhibition of (2) are improved, and the FeS is improved 2 The cycling stability and rate capability of the @ C material. Internal polynuclear FeS 2 The particles also facilitate the exposure of more active sites and the full exertion of the active substances. In addition, after the internal structure is optimized by adjusting the etching time, the infiltration of the electrolyte is promoted, the diffusion distance of electrons and ions is shortened, and the integral potassium storage performance is improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: MCS-FeS prepared by the method of the invention 2 The @ C-20 material shows excellent electrochemical performance as a negative electrode material of a potassium ion battery, and MCS-FeS 2 @ C-20 at 50mA g -1 At a current density of 519mAh g -1 Reversible capacity. At 5A g -1 Can still provide 107mAh g under a large multiplying power -1 Reversible capacity at 500mA g -1 The high-capacity lithium ion battery has good cycle stability in 500 cycles under current density, and the capacity retention rate is 84.3%. Furthermore, MCS-FeS 2 @C-20//K 0.4 CoO 2 The total potassium ion battery is 50mA g -1 Exhibits a reversible capacity of 251mAh g at current density -1 The capacity retention after 200 cycles can reach 216mAh g -1 . Thus, this MCS-FeS 2 The @ C-20 material has good application potential as a high-performance low-cost cathode material.
Drawings
FIG. 1 shows MCS-FeS of embodiment 1 of the present invention 2 The XRD pattern of the @ C-20 material;
FIG. 2 shows MCS-FeS of embodiment 1 of the present invention 2 XPS plots of the @ C-20 material;
FIG. 3 shows MCS-FeS of embodiment 1 of the present invention 2 Thermogram of @ C-20 material;
FIG. 4 shows MCS-FeS of embodiment 1 of the present invention 2 The @ C-20 material has a nitrogen adsorption and desorption curve and an aperture distribution diagram, wherein a is a nitrogen adsorption-desorption isotherm, and b is a corresponding aperture distribution diagram;
FIG. 5 shows MCS-FeS of embodiment 1 of the present invention 2 SEM pictures of the @ C-20 material, where a is a low power SEM picture and b is an enlarged SEM picture;
FIG. 6 shows MCS-FeS of embodiment 1 of the present invention 2 TEM images of the material @ C-20, where a is a low magnification TEM image and b is an enlarged TEM image;
FIG. 7 shows MCS-FeS of embodiment 1 of the present invention 2 Cyclic voltammogram of the @ C-20 electrode;
FIG. 8 shows MCS-FeS of embodiment 1 of the present invention 2 The charge/discharge curve of the @ C-20 electrode;
FIG. 9 shows an embodiment of the present inventionMCS-FeS of example 1 2 Rate performance plots for the materials of @ C-20 and the comparative example at different current densities;
FIG. 10 shows MCS-FeS of embodiment 1 of the present invention 2 @ C-20 and comparative materials at 50mA g -1 A plot of cycling performance at current density;
FIG. 11 shows MCS-FeS of embodiment 1 of the present invention 2 @ C-20 electrode at 500mA g -1 A plot of cycling performance at current density;
FIG. 12 shows MCS-FeS of embodiment 2 of the present invention 2 SEM pictures of the @ C-10 material, where a is a low power SEM picture and b is an enlarged SEM picture;
FIG. 13 is MCS-FeS of embodiment 3 of the present invention 2 SEM pictures of the material @ C-30, where a is a low-magnification SEM picture and b is an enlarged SEM picture;
FIG. 14 is a comparative example of pure-FeS of the present invention 2 SEM images of the materials, wherein a is a low-magnification SEM image and b is an enlarged SEM image.
Detailed Description
Example 1
FeS with multi-core-shell structure 2 Preparation of @ C nanocapsule material:
(1) 5mL of sodium hydroxide solution (6M) was slowly added to 5mL of iron trichloride solution (2M), and the mixture was heated and stirred at 70 ℃ for 5 minutes. Then adding 40mg ammonium sulfate, stirring uniformly, reacting for 6 days at 100 ℃, centrifuging the precipitate, washing with water for 3 times, washing with ethanol for 3 times, and drying at 70 ℃ to obtain Fe 2 O 3 Nano-capsule particles;
(2) adding the product obtained in the step (1) and 175mg of dopamine hydrochloride into 410ml Tris buffer solution, stirring for 2 hours, centrifuging, washing, and drying at 70 ℃. Sintering the product for 3 hours at 600 ℃ in argon to obtain Fe 3 O 4 @ C nanocapsules;
(3) adding 4mmol L of the product obtained in the step (2) -1 Stirring the HF diluent for 20 minutes, centrifuging, washing with water for 3 times, washing with ethanol for 3 times, and drying at 70 ℃;
(4) drying the product obtained in the step (3), pressing the product into powder, putting the powder into a tube furnace, and putting the powder into the tube furnace in H 2 At 2 deg.C for min in S/Ar (volume ratio of 10: 90) -1 After the temperature is raised to 350 ℃ at the rate of4 hours to obtain the final product, and since the HF etching time is 20 minutes, the sample is marked as MCS-FeS 2 @C-20。
MCS-FeS 2 Characterization of the @ C-20 material:
FIG. 1 shows MCS-FeS 2 The XRD spectrum of the @ C-20 material indicates that the material is phase-pure FeS 2 A compound; FIG. 2 shows MCS-FeS 2 The XPS survey of @ C-20, which shows the presence of Fe, S, O, N and C elements; FIG. 3 is a diagram of MCS-FeS 2 Thermogram of @ C-20 demonstrating FeS therein 2 The content of (A) is 69.8%; FIG. 4 is a MCS-FeS 2 The nitrogen desorption curve and corresponding pore size distribution plot of @ C-20, which indicates MCS-FeS 2 Specific surface area of @ C-20 Material is 79.2m 2 g -1 The pore size of the mesopores is concentrated at 3.7 and 8.8 nm.
The resulting MCS-FeS was analyzed using SEM and TEM images 2 The size, morphology and microstructure of the @ C-20 material. FIGS. 5a and 5b are MCS-FeS 2 SEM picture of @ C-20, FIG. 4a shows MCS-FeS 2 The @ C-20 material integrally presents a uniform multi-core shell capsule structure; FIG. 5b shows MCS-FeS 2 @ C-20 consisting of an external conductive carbon shell and an internal FeS 2 The core composition was about 800nm in length and about 330nm in width. FIGS. 6a and b are MCS-FeS 2 TEM image of @ C-20. FIG. 6a also shows a multiple core-shell capsule structure; FIG. 6b is MCS-FeS 2 Partial magnified TEM image of @ C-20 showing MCS-FeS 2 FeS inside @ C-20 2 Showing a sparsely porous state.
And (3) electrochemical performance testing:
MCS-FeS prepared in this example was dissolved in 1-methyl-2-pyrrolidone 2 @ C-20, carbon black and polyvinylidene fluoride are ground and mixed uniformly according to the mass ratio of 80: 10, the obtained uniform slurry is coated on a Cu foil and is dried for 12 hours in vacuum at 80 ℃. Using 3mol L -1 A1, 2-Dimethoxyethane (DME) solution of KFSI is used as a potassium ion battery electrolyte, and glass fiber and metal potassium are respectively used as a potassium ion battery diaphragm and a counter electrode. The electrochemical performance was tested using a CR2032 cell. The cell assembly was carried out in a glove box filled with argon atmosphere, both water and oxygen concentrations being less than 0.1 ppm.Constant current charge and discharge test of battery at room temperature, using blue CT2001A multi-channel battery test system, at 0.01-3.0V (vs.K) + and/K) in a fixed voltage range. Specific properties are shown in fig. 7 to 10.
FIG. 7 is MCS-FeS 2 @ C-20 electrode at 0.01-3.0V (vs. K) + K) voltage interval, scan rate of 0.1mV s -1 The peak of 0.78V appearing in the first circulation process of the cyclic voltammetry curves of the first three circles can be attributed to the formation of a solid electrolyte membrane, and then the curves are basically superposed, which shows that the reversibility of the material in potassium intercalation is good; FIG. 8 is MCS-FeS 2 @ C-20 at 0.01-3.0V (vs. K) + /K) charging/discharging curve of voltage interval with current density of 50mA g -1 The first discharge and charge specific capacities are 917 mAh g and 519mAh g, respectively -1 The voltage plateau corresponds to the redox peak of the cyclic voltammogram; FIG. 9 is MCS-FeS 2 @ C-20 and comparative pure FeS 2 The graph of the rate performance at different current densities, it can be seen that even at 5A g -1 At high current density of (C), MCS-FeS 2 The @ C-20 capacity can still reach 107mAh g -1 Is obviously higher than pure FeS 2 (ii) a FIG. 10 shows MCS-FeS 2 @ C-20 and comparative pure FeS 2 At 50mA g -1 The cyclic performance diagram at current density, obviously, MCS-FeS 2 The @ C-20 capacity is higher and the cycle is stable; FIG. 11 shows MCS-FeS 2 @ C-20 at 500mA g -1 Graph of cycling performance at current density, showing MCS-FeS 2 After 420 cycles of @ C-20 cycle, the capacity retention rate reaches 84.3 percent.
Example 2
(1) 5mL of sodium hydroxide solution (6M) was slowly added to 5mL of iron trichloride solution (2M), and the mixture was heated and stirred at 70 ℃ for 5 minutes. Then adding 40mg ammonium sulfate, stirring uniformly, reacting for 6 days at 100 ℃, centrifuging the precipitate, washing with water for 3 times, washing with ethanol for 3 times, and drying at 70 ℃ to obtain Fe 2 O 3 Nano-capsule particles;
(2) adding the product obtained in the step (1) and 175mg of dopamine hydrochloride into 410ml Tris buffer solution, stirring for 2 hours, centrifuging, washing, and drying at 70 ℃. Sintering the product for 3 hours at 600 ℃ in argon to obtain Fe 3 O 4 @ C sodiumRice capsules;
(3) adding 4mmol L of the product obtained in the step (2) -1 Stirring the HF diluent for 10 minutes, centrifuging, washing with water for 3 times, washing with ethanol for 3 times, and drying at 70 ℃;
(4) drying the product obtained in the step (3), pressing the product into powder, putting the powder into a tube furnace, and putting the powder into a tube furnace in H 2 At 2 deg.C for min in S/Ar (volume ratio of 10: 90) atmosphere -1 Heating to 350 deg.C, maintaining for 4 hr to obtain final product, and marking the sample as MCS-FeS due to HF etching time of 10 min 2 @C-10。
The obtained MCS-FeS was subjected to the same treatment as in example 1 2 The @ C-10 material is subjected to structural characterization and electrochemical performance test. The morphology is shown in FIG. 12, MCS-FeS 2 The entirety of @ C-10 exhibited a uniform multi-shelled capsule structure, but the internal FeS 2 More particles, close packing among particles and smaller internal space. The results of the electrochemical performance test are shown in Table 1.
Example 3
(1) 5mL of sodium hydroxide solution (6M) was slowly added to 5mL of iron trichloride solution (2M), and the mixture was heated and stirred at 70 ℃ for 5 minutes. Then adding 40mg ammonium sulfate, stirring uniformly, reacting for 6 days at 100 ℃, centrifuging the precipitate, washing with water for 3 times, washing with ethanol for 3 times, and drying at 70 ℃ to obtain Fe 2 O 3 Nano-capsule particles;
(2) adding the product obtained in the step (1) and 175mg of dopamine hydrochloride into 410ml Tris buffer solution, stirring for 2 hours, centrifuging, washing, and drying at 70 ℃. Sintering the product for 3 hours at 600 ℃ in argon to obtain Fe 3 O 4 @ C nanocapsules;
(3) adding 4mmol L of the product obtained in the step (2) -1 Stirring the HF diluent for 30 minutes, centrifuging, washing with water for 3 times, washing with ethanol for 3 times, and drying at 70 ℃;
(4) drying the product obtained in the step (3), pressing the product into powder, putting the powder into a tube furnace, and putting the powder into the tube furnace in H 2 At 2 deg.C for min in S atmosphere -1 Heating to 350 deg.C, maintaining for 4 hr to obtain final product, and marking the sample as MCS-FeS due to HF etching time of 30min 2 @C-30。
According to the combination of the ingredientsExample 1 the same procedure was carried out on the obtained MCS-FeS 2 The @ C-30 material is subjected to structural characterization and electrochemical performance test. The morphology is shown in FIG. 12, MCS-FeS 2 The entirety of @ C-30 exhibits a uniform multi-core shell capsule structure, but internal FeS 2 The particles are fewer, the accumulation among the particles is very sparse, and the internal space is larger. The results of the electrochemical performance test are shown in Table 1.
Comparing the electrochemical performance of examples 1, 2 and 3, it is seen that FeS prepared in example 1 after etching with HF diluent for 20 minutes 2 The @ C sample has better performance. The length of the etching time can affect the size of the space inside the final product core-shell structure. The product obtained by etching for 10 minutes has small internal space and FeS 2 The particles are numerous, and the volume change generated in the circulation process is easy to damage the material structure. And FeS inside the final product after 30 minutes etching 2 Too little active material, showing a lower reversible capacity. After an etching time of 20 minutes, the final product possessed the appropriate internal space and active species. This ensures both a high output capacity and maintains structural integrity.
Comparative example 1
Pure FeS 2 Preparation of the material:
(1) 100mg of Fe was weighed 3 O 4 Placing in a mortar, and grinding for 10 minutes to obtain Fe with small particles 3 O 4 ;
(2) Putting the product obtained in the step (1) in a tube furnace, and introducing H 2 S gas, 2 ℃ min -1 The temperature is raised to 350 ℃ at the rate of (1) and then kept for 4 hours to obtain the final product.
The pure FeS thus obtained was purified in the same manner as in example 1 2 And carrying out structural characterization and electrochemical performance test. The morphology is shown in FIG. 14, pure FeS 2 The material is irregular particles of about 500 nm. FIG. 9 shows pure FeS 2 And MCS-FeS 2 Rate performance diagram of @ C-20 at different current densities, MCS-FeS 2 The reversible capacity of @ C-20 is obviously higher than that of pure FeS 2 (ii) a FIG. 10 shows pure FeS 2 And MCS-FeS 2 @ C-20 at 50mA g -1 Comparison of the cycle performance at Current Density, which shows pure FeS 2 Has a cycle stability far behind that of MCS-FeS 2 @ C-20; from the above tests, pure FeS 2 The electrochemical performance is far lower than that of MCS-FeS 2 @C-20。
TABLE 1 electrochemical Performance data
Claims (10)
1. FeS with multi-core shell structure 2 The preparation method of the @ C nano capsule material is characterized by comprising the following steps of:
(1) fe production using ammonium sulfate-assisted hydrothermal process 2 O 3 A nanocapsule template;
(2) covering polydopamine on the surface of the product obtained in the step (1), and sintering in argon to obtain Fe 3 O 4 @ C nanocapsules;
(3) treating the product obtained in the step (2) by using HF diluent, stirring and centrifuging to obtain the Fe with the multi-core shell structure 3 O 4 @ C nanocapsules;
(4) subjecting the product of step (3) to reaction in H 2 Calcining in S atmosphere to obtain FeS with a multi-core shell structure 2 @ C nanocapsule material.
2. FeS of multi-core shell structure according to claim 1 2 The preparation method of the @ C nanocapsule material is characterized in that ammonium sulfate is added into the hydrothermal solution in the step (1).
3. FeS of multi-core shell structure according to claim 1 2 The preparation method of the @ C nanocapsule material is characterized in that the hydrothermal temperature in the step (1) is 80-100 ℃ and the hydrothermal time is 4-6 days.
4. The multi-core of claim 1FeS of shell structure 2 The preparation method of the @ C nanocapsule material is characterized in that Fe in the step (2) 2 O 3 The concentration of the dispersion is 5-8 mmol L -1 。
5. FeS of multi-core shell structure according to claim 1 2 The preparation method of the @ C nanocapsule material is characterized in that the carbonization temperature in argon in the step (2) is 600-700 ℃.
6. FeS of multi-core shell structure according to claim 1 2 The preparation method of the @ C nanocapsule material is characterized in that the concentration of the HF diluent in the step (3) is 2-4 mmol L -1 。
7. FeS of multi-core shell structure according to claim 1 2 The preparation method of the @ C nanocapsule material is characterized in that the step (3) is carried out by magnetic stirring for 10-30 min.
8. FeS of multi-core shell structure according to claim 1 2 The preparation method of the @ C nanocapsule material is characterized in that the calcination atmosphere in the step (4) is H 2 The volume ratio of the S/Ar mixed gas is 10: 90.
9. FeS of multi-core shell structure according to claim 1 2 The preparation method of the @ C nanocapsule material is characterized in that the calcination temperature in the step (4) is 300-400 ℃ and the calcination time is 3-5 hours.
10. FeS with multi-core shell structure prepared by the method of any one of claims 1-9 2 The application of the @ C nanocapsule material as a potassium ion battery negative electrode material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210382823.XA CN114824202B (en) | 2022-04-12 | 2022-04-12 | FeS with multi-core shell structure 2 Preparation method and application of @ C nanocapsule material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210382823.XA CN114824202B (en) | 2022-04-12 | 2022-04-12 | FeS with multi-core shell structure 2 Preparation method and application of @ C nanocapsule material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114824202A true CN114824202A (en) | 2022-07-29 |
CN114824202B CN114824202B (en) | 2023-08-22 |
Family
ID=82535120
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210382823.XA Active CN114824202B (en) | 2022-04-12 | 2022-04-12 | FeS with multi-core shell structure 2 Preparation method and application of @ C nanocapsule material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114824202B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115636443A (en) * | 2022-10-27 | 2023-01-24 | 郑州航空工业管理学院 | Preparation method of magnetic nanoparticle coated microcapsule-shaped carbon-based composite material |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06122519A (en) * | 1991-05-27 | 1994-05-06 | Toda Kogyo Corp | Hydrated amorphous ferric oxide particle powder and its production |
CN1364730A (en) * | 2002-02-08 | 2002-08-21 | 无锡威孚吉大新材料应用开发有限公司 | Method for preparing super-fine nanometer ferric oxide powder |
EP2955775A1 (en) * | 2014-06-10 | 2015-12-16 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Berlin | Method of fabricating mesoporous carbon coated FeS2, mesoporous carbon coated FeS2, positive electrode material |
US20160260964A1 (en) * | 2013-09-16 | 2016-09-08 | Colorado School Of Mines | Lithium ion battery cathode material |
CN105990560A (en) * | 2015-02-09 | 2016-10-05 | 北京大学 | Iron oxide porous nanorod array electrode material and preparation method thereof |
CN106848301A (en) * | 2017-03-10 | 2017-06-13 | 三峡大学 | A kind of Fe2O3Nano-bar array electrode is In-situ sulphiding and preparation method and applications of carbon coating |
CN107275624A (en) * | 2017-07-24 | 2017-10-20 | 扬州大学 | The preparation method of carbon coating spindle shape iron oxide composite material of core-shell structure |
CN108987718A (en) * | 2018-07-24 | 2018-12-11 | 西南科技大学 | High performance lithium ionic cell cathode material, that is, core-shell structure FeS2The preparation method of@C nano ring |
CN110655807A (en) * | 2019-09-29 | 2020-01-07 | 江西金环颜料有限公司 | Preparation method of zirconium silicate coated iron oxide red for ceramic ink-jet printing |
CN113036121A (en) * | 2021-03-05 | 2021-06-25 | 大连理工大学 | Carbon-coated transition metal sulfide nanoflower structure, preparation method and application thereof |
CN113184914A (en) * | 2021-04-20 | 2021-07-30 | 广东工业大学 | Porous capsule-shaped Fe2O3Nano material and preparation method and application thereof |
-
2022
- 2022-04-12 CN CN202210382823.XA patent/CN114824202B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06122519A (en) * | 1991-05-27 | 1994-05-06 | Toda Kogyo Corp | Hydrated amorphous ferric oxide particle powder and its production |
CN1364730A (en) * | 2002-02-08 | 2002-08-21 | 无锡威孚吉大新材料应用开发有限公司 | Method for preparing super-fine nanometer ferric oxide powder |
US20160260964A1 (en) * | 2013-09-16 | 2016-09-08 | Colorado School Of Mines | Lithium ion battery cathode material |
EP2955775A1 (en) * | 2014-06-10 | 2015-12-16 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Berlin | Method of fabricating mesoporous carbon coated FeS2, mesoporous carbon coated FeS2, positive electrode material |
CN105990560A (en) * | 2015-02-09 | 2016-10-05 | 北京大学 | Iron oxide porous nanorod array electrode material and preparation method thereof |
CN106848301A (en) * | 2017-03-10 | 2017-06-13 | 三峡大学 | A kind of Fe2O3Nano-bar array electrode is In-situ sulphiding and preparation method and applications of carbon coating |
CN107275624A (en) * | 2017-07-24 | 2017-10-20 | 扬州大学 | The preparation method of carbon coating spindle shape iron oxide composite material of core-shell structure |
CN108987718A (en) * | 2018-07-24 | 2018-12-11 | 西南科技大学 | High performance lithium ionic cell cathode material, that is, core-shell structure FeS2The preparation method of@C nano ring |
CN110655807A (en) * | 2019-09-29 | 2020-01-07 | 江西金环颜料有限公司 | Preparation method of zirconium silicate coated iron oxide red for ceramic ink-jet printing |
CN113036121A (en) * | 2021-03-05 | 2021-06-25 | 大连理工大学 | Carbon-coated transition metal sulfide nanoflower structure, preparation method and application thereof |
CN113184914A (en) * | 2021-04-20 | 2021-07-30 | 广东工业大学 | Porous capsule-shaped Fe2O3Nano material and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
YONG WANG等: "Shape-controlled synthesis of TiO2 hollow structures and their application in lithium batteries", vol. 22, no. 22, pages 1969 - 1976 * |
翁网所: "铁基复合物用作碱金属离子电池负极材料研究", pages 042 - 781 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115636443A (en) * | 2022-10-27 | 2023-01-24 | 郑州航空工业管理学院 | Preparation method of magnetic nanoparticle coated microcapsule-shaped carbon-based composite material |
Also Published As
Publication number | Publication date |
---|---|
CN114824202B (en) | 2023-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111362254B (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
CN108269982B (en) | Composite material, preparation method thereof and application thereof in lithium ion battery | |
CN109399601B (en) | Preparation method and application of nitrogen-phosphorus co-doped biochar material | |
CN109768260B (en) | Cobaltoside/carbon composite material and preparation method and application thereof | |
CN109888247B (en) | Preparation method of lithium zinc titanate/carbon nano composite negative electrode material for lithium ion battery | |
CN113401897B (en) | Preparation method of black phosphorus-based graphite composite lithium ion battery negative electrode material | |
CN109037632A (en) | A kind of nano lithium titanate composite material and preparation method, lithium ion battery | |
CN112357956A (en) | Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof | |
CN111740110A (en) | Composite negative electrode material, preparation method thereof and lithium ion battery | |
CN111564610A (en) | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof | |
CN114824202B (en) | FeS with multi-core shell structure 2 Preparation method and application of @ C nanocapsule material | |
CN114464780A (en) | Nano-core-shell-inlaid nano-sheet-shaped ion battery negative electrode composite material and preparation method and application thereof | |
CN111725492B (en) | Carbon/lithium titanate composite material and preparation method thereof | |
CN111554905B (en) | Preparation method, product and application of zinc oxide-based carbon composite nano material | |
CN111740084B (en) | Sulfur-doped pre-lithiated silicon-carbon composite material and preparation method thereof | |
CN110600710B (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
CN112421002B (en) | High-capacity silicon-carbon material and preparation method thereof | |
CN110429266B (en) | Lithium ion battery anode material and preparation method thereof | |
CN114156482A (en) | Preparation method of nano-diamond electrolyte and nano-diamond solid electrolyte interface | |
CN113903915A (en) | Preparation method of graphene-coated porous lead oxide-lead sulfide composite material | |
CN113410460A (en) | Three-dimensional ordered macroporous carbon-coated nickel selenide nanocrystalline material, preparation and application | |
CN112374552A (en) | Composite modified graphite negative electrode material and preparation method thereof | |
CN112582616B (en) | FeSz-FexOyCore-shell structure composite material and preparation method and application thereof | |
CN114242982B (en) | Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof | |
CN113299895B (en) | Controllable synthesis and energy storage application of cake-shaped sulfur-based compound composite material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |